Acrylic and methacrylic monomers

ABSTRACT

A NEW CLASS OF POLYMERS COMPRISING A MAIN CARBON CHAIN AND HAVING POLYFLUOROPOLYETHER SIDE GROUPS. THE POLYMERS POSSESS EXCELLENT SOIL AND WATER RESISTANT PROPERTIES AND ARE USEFUL FOR RENDERING FABRICS SOIL AND MOISTURE RESISTANT. THE POLYMERS ARE PREPARED FROM A NEW CLASS OF POLYMERIZABLE POLYFLUORINATED POLYETHER ACRYLATES, METHACRYLATES, ACRYLAMIDES AND METHACRYLAMIDES. A NEW CLASS OF ALCOHOLS, USEFUL FOR PREPARING THE ACRYLATE AND METHACRYLATE MONOMERS IS DISCLOSED AND METHODS FOR PREPARING THE ALCOHOLS, MONOMRS AND POLYMERS ARE DISCLOSED.

United States Patent 01 fice 3,766,251 Patented Oct. 16, 1973 3,766,251ACRYLIC AND METHACRYLIC MONOMERS Gerardo Caporiccio, Milan, and EzioStrepparola, Treviglio, Italy, assignors to Montecatini Edison S.p.A.,Milan, Italy No Drawing. Filed Jan. 21, 1971, Ser. No. 108,573 Claimspriority, application Italy, Jan. 24, 1970, 19,750/70 Int. Cl. C07c69/54 U.S. Cl. 260-486 H 4 Claims ABSTRACT OF THE DISCLOSURE A new classof polymers comprising a main carbon chain and havingpolyfluoropolyether side groups. The polymers possess excellent soil andwater resistant properties and are useful for rendering fabrics soil andmoisture resistant. The polymers are prepared from a new class ofpolymerizable polyfluorinated polyether acrylates, methacrylates,acrylamides and methacrylamides. A new class of alcohols, useful forpreparing the acrylate and methacrylate monomers is disclosed andmethods for preparing the alcohols, monomers and polymers. aredisclosed.

BACKGROUND OF THE INVENTION (1) Field of the invention The presentinventioin relates to a new class of monomeric acrylic and methacrylicderivatives of compounds having a linear polyfiuoropolyether structure,and to homopolymers and copolymers thereof. These monomeric compoundscan be polymerized to form elastomeric polymers possessing manydesirable properties by virtue of the polyfluoroether structure which ispresent as a side chain group on the main polymer chain.

(2) Description of the prior art Polymers derived from olefinic monomersand having fluorine-containing side groups attached to the main carbonchain are known. Such polymers frequently have certain desirableproperties. For example, they are normally elastomers or rubberypolymers which can be vulcanized to produce rubbers having lowtemperature flexibility, excellent resistance to oxidation by air,resistance to oils and lubricants, etc.

A polymer of this type is illustrated in British Pat. 703,- 435 whereinthe polymerization of an ester of acrylic acid and a1,1-dihydroperfiuoroalkyl alcohol is disclosed. U.S. Pat. 2,839,513,discloses fiuorinated acrylate esters which can be used to prepare theforegoing described polymers, which esters contain a terminallyhydrogenated carbon atom and an oxa atom, i.e., an oxygen atom in placeof a carbon atom in the carbon chain of the fiuoropolymer. Such estersare illustrated by the compound 1,1,6-trihydro- 4-oxa-perfluorohexylacrylate.

In U.S. Pat. 2,826,584, normal3-perfluoroalkoxy-l,ldihydroperfluoropropyl acrylates containing 3 to 6fully fiuorinated carbon atoms in the molecule are described. Thesemonomers do not contain the terminally hydrogenated carbon atom but dopossess an oxa oxygen atom in the fluorocarbon chain.

SUMMARY OF THE INVENTION We have discovered a new class of linearpoly-perfluoropolyether monomers which can be polymerized to formelastomers.

More particularly, the monomers of the present invention comprisepolyfluorinated polyether acrylates, methacrylates, acrylamides andmethacrylamide of the formula:

wherein:

C 1 represents a group obtained by the opening of the double bond of ahexafiuoropropylene molecule,

-C 'F O and CF O are repeating oxyperfluoroalkylene units which, whensimultaneously present, are distributed randomly along the chain,

In and n may be zero or integers from 1 to 20 with the proviso that nand m cannot both be zero at the same time,

the sum of m+n is an integer from 1 to 20,

A is a CF or CF O-CF(CF )-terminal group,

Z is CX(Y)O or CH NR' wherein X is a hydrogen or fluorine atom, Y is aCF group or may be hydrogen but only when X is also hydrogen, and

R and R are the same or different and are hydrogen or Additionally, wehave discovered a new class of primary and secondary polyfluorinatedpolyether alcohols which can be used to prepare the monomers of thepresent invention. These alcohols have the formula:

group, and wherein A, m andn are as above defined.

We have further discovered a new class of elastomeric polymers and amethod for preparing such polymers using the monomers of the presentinvention.

The polymers of the acrylates, methacrylates, acrylamides andmethacrylamides of the present invention possess varying molecularweights, depending on the conditions under which the polymer isobtained. The molecular weights, as determined by measurement of theintrinsic viscosity, can vary from a value from about ten thousand toseveral hundreds of thousands.

These polymers are elastomers and exhibit a range of useful properties.Such polymers are highly flexible at temperatures as low as or lowerthan C., and possess excellent resistance to thermal degradation even inthe presence of air at temperatures up to 250 C., excellentoil-repelling properties and resistance to attack by mineral andvegetable oils, a high insolubility in all of the common organicsolvents, a high resistance to oxidizing agents, and excellent physicalsurface properties resulting in surprisingly low values of the criticalsurface tension of wettability of films prepared from such polymers.

The polymers of the present invention are particularly suitable forimparting soil and moisture resistance to fabrics. Usually, the fabricis impregnated with the polymer of the present invention. Methods foraccomplishing such impregnation are well known in the art, the mostcommon being simply dipping the fabric in a solution of the polymer in asuitable solvent and drying the fabric.

Fabrics treated in this manner with the polymers of the presentinvention not only exhibit high initial water, oil and soil resistance,but also retain the high levels of resistance after repeated washings.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred acrylate andmethacrylate monomers of the present invention may be represented by theformula:

A-O (C F O) (CF O) ,,CF

CX(Y)O-COCR=CH (3) wherein A, X, Y, R, rm and n are as definedhereinabove. The above esters are prepared by esterifying acrylic or'methacrylic acid with an alcohol of Formula 2 hereinabove. The alcoholshaving this structure are new compositions and include the followingpreferred alcohols,

as well as homologous products of higher molecular weight, and mixturesthereof:

CF=O OF -CFO CFzCHgOH Fl1.1-dihydro-3,6-dioxa-4-perfiuoromethyl-octafluoroheptanol l C F140 OF-C F O gC FICII OII 1,1dlhydro-3,6,9trloza-t,7-diperfluoro1nethylundecafluoro-decanol-l1,1-dlhydro-3,G,9,12-tetraoxa4,7,10-triperfiuoromethyltetradecafluorotridecanol-12-hydro-4,7,9tr1oxa-5,8-diperfluoromethyl-dodecafluorodecanol-22-hydro-4,7 ,10-trioxa5,8-diperfiuoromethyl-tetradecafluoroundecanol-Z2-hydro-4,7,10,13-tetraoxa-5,8,ll-triperfinorometllylheptadecafluor-tetradecano1-2B-l1ydr04,7,10,12tetraoxa-5,S-diperfiuor0met11y1hexadecafluoro-tridecanol-2CF30 CF C FzCHgOH 1,1-d1hydro-3,fi-dioxa-heptafluoro-hexanol-lomowmon-omomorr 1,1-dihydro-3,5,7-tr1oxa-nonafluoro-octanoL1 CFa0(OFO)3-CF CH OH 1,1-dihydro-3,5,7,9-tetraoxa-undecafiuoro-decanol-1CFaO(CFzO)4-CF CHaOI-I1,1-(lil1y(lro-3,5,7,9,ll-pentaoxa-tridecafiuoro-dodecanol-l The acrylicand methacrylic esters of Formula 3 and which are derived from theprimary or secondary alcohols of Formula 2, can be obtained by using anyone of various conventional methods known in the esterification art.Such methods are described, for example, by R. B. Wagner and H. D. Zook,in Synthetic Organic Chemistry, J. Wiley, New York, 1956, page 479.

In particular, the direct esterification of the methacrylic acid can becarried out with the alcohols of Formula 2 in the presence of a catalystin an amount between about 0.01 and 5 parts per 100 parts by weight, thecatalyst being a strong acid such as sulfuric acid or hydrochloric acid.Alternatively, the esterification can be performed by removing the waterproduced by the esterification by azeotropically distilling it in thepresence of benzene, methylene chloride or chloroform.

The esterification can also be effected by reacting the primary orsecondary alcohols with acrylyl or methacrylyl chloride. In this casethe esterification can be carried out in the presence or absence of anagent capable of neutralizing the hydrochloric acid produced, e.g.,pyridine, triethylamine, or the like.

The present esters can also be obtained by transesterification ofmethylacrylate or methymethacrylate with the primary or secondarypolyfiuorinated alcohols of Formula 2. The transesterification can beconducted by operating in the presence of an excess of the fluorinatedalcohol and in the absence of solvents and catalysts, and by removingthe methanol formed by distillation.

Alternatively, the transesterification is preferably carried out in thepresence of catalysts such as the mercuric salts, antimonous trioxide orthe titanium tetraalcoholates such as, for example, Tl(OlC3H7)4, inamounts between about 0.1 and 5 parts by weight per parts of fluorinatedalcohol. The reaction can also be carried out in a dissolving ordispersing medium such as benzene or toluene.

Also within the scope of Formula 3 are those acrylates and methacrylateswhich would appear, on the basis of their structural formulas, to be theproducts of secondary perfluoropolyether alcohols of the formula:

These alcohols, however, are unstable and do not appear in the freestate. The acrylates and metacrylates of such' perfluoro-alcohols may,however, be obtained by using the technique described by A. G. Pittmanet al. in American Chemical Society, Polymer Preprints, September 1966,7 (2), 1093. As described therein, perfiuorinated polyether ketones ofthe formula wherein A, m and n are as defined above are reacted in anaprotic solvent medium with a stoichiometric amount of an alkalifluoride and then with an acrylyl or methacrylyl chloride or bromide.

The alkali fluoride (represented by MP) is normally dispersed in anaprotic solvent such as an aliphatic or cycloaliphatic ether, e.g.,ethyl ether, butyl ether, dimethoxyethane, dioxane, tetrahydrofuran oracetonitrile or N, N-dimethylformamide, and is then reacted with thepolyether ketone.

An intermediate secondary alkali perfluoro alcoholate is obtained havingthe structure:

F 3 6 )m(CFQO) OFZ JJO M r wherein: M+ may be a K Na+ or Ca+ ion andwherein A, m and n are as defined above.

The reaction is carried out at temperatures between 0 C. and 100 C., andpreferably between about 0 C. and 50 C.

The acrylyl or methacrylyl chloride or bromide is then added to thisorganic suspension at a temperature between about 0 C. and 20 C. andthereafter the reaction is carried to completion at a temperaturebetween about 20 C. and 100 C., to give the esters of the secondaryperfluoro alcohols.

The primary and secondary polyfluorinated polyether alcohols of theFormula 2 can be prepared by chemical reduction of perfluorinatedpolyether compounds of the formula:

A-O(C F O) (CF O) B (7) wherein: B is either a CF --COCF or a CF -COORgroup wherein R is a hydrogen atom or an alkyl group containing from 1to 3 carbon atoms, and the other groups and indices are as definedabove.

Various suitable methods may be used to obtain these polyfluoropolyetheralcohols from the corresponding compounds of Formula 7, for example asdescribed by A. M. Lovelace, D. A. Rausch and W. Postelnek in AliphaticFluorine Compounds, Reinhold P.C., New York 1958 (page 137 and seq.),and by M. Hudlicky in Chemistry of Organic Fluorine Compounds, PergamonPress, London 1961 (page 157 and seq.).

Suitable reducing agents for this reaction are: molecular hydrogen inthe presence of catalysts consisting of metals of Group VIII of thePeriodic Table of Elements, preferably those of the group comprising Ni,Co, Pd, Pt, Ru, Os, and Ir. These metals may be used in a finely dividedstate either alone or supported on inert materials such as carbon ordiatomite. Additionally, the metals 5 may be in the form of their oxidessuch as, e.g., Adams platinum catalyst.

The reduction may be carried out in the presence or absence of liquidsolvent or dispersing media such as ethers, cyclic and linearpolyethers, acetic acid, alcohols, water, and aliphatic orcycloaliphatic hydrocarbons.

The reaction conditions generally include temperatures between about C.and 250 C., preferably between 20 and 200 C. The hydrogen pressure canvary between about and 200 atm. and preferably between about and 100atm.

Alternatively, the reduction may be carried out in the presence ofcomplex alkali boron, or aluminum tetrahydrides such as, for example,LiBH NaBH LiAlH at temperatures between about 0 C. and 100 C. and in thepresence of ethyl ether, dioxane, dimethoxyethane or. when NaBH is thecatalyst, water or methanol.

The acrylamides and the methacrylamides of the present invention havethe following structural formula:

wherein: A, R, R, m and n are as defined above.

These compounds are obtained by reacting either the esters of Formula 7wherein B is CF COOR or the halides of the corresponding carboxylicacids to transform the terminal functional group, i.e. COOR or COHal, toan aminic group, and subsequently reacting the amine to obtain therespective acrylamides or methacrylamides.

Specifically, the acid or ester is converted to an amide or amonoalkalylamide and the amide or the monoalkylamide is then chemicallyreduced, respectively, to the amine or a monoalkylamine. Finally theselatter two compounds are transformed into the desired acrylamides ormethacrylamides.

The foregoing described reactions are illustrated by the followingreaction sequence:

R'NH2 reduction -wCP COW MCFQCONHRI wherein R and R are as definedabove, and W represents a halogen atom or an alkoxy group, such as,e.g., CH O 0r C2H5O'.

The amidation reaction, reduction of the amid-e into a primary orsecondary amine, and the transformation of this latter compound into anacrylic derivative, can be carried out according to conventional methodsdescribed, for instance, by A. B. Wagner and M. P. Zook, in SyntheticOrganic Chemistry, I. Wiley, New York (1953) and by A. M. Lovelace, D.A. Rausch, and W. Postelnek, in Aliphatic Fluorine Compounds, ReinholdP.C., New York (1958). More particularly, the amides or the N-alkylamides of these perfluorinated acids can be prepared inquantitative yields, starting from the acyl chlorides or fluoridesthereof or from the esters thereof, by reacting these compounds withgaseous ammonia or with primary amines, in the absence or presence ofsolvents such as aliphatic or alicyclic ethers, at temperatures fromabout 0 C. to about 30 C.

The reduction of the amides into amines can be carried out, usually withvery high or quantitative yields, by means of alkali boron or aluminumtetrahydrides, such as LiAlH in an ethyl ether solution at temperaturesbetween about 0 C. and 30 C. The primary and secondary amines obtainedreact easily and quantitatively with the acrylyl or methacrylyl chloridein ethyl ether solutions and in the presence of a basic substance, suchas triethylamine or pyridine.

The polyether perfluoroketones, perfluoroacids and perfluoroesters ofFormula 7 may be obtained by the methods described in Italian Pats. Nos.789,221, 773,214, 774,001 and 773,920.

The acrylates, methacrylates, acrylamides and methacrylamides of thepresent invention are easily polymerized by free radical polymerization.Bulk polymerization as well as polymerization in solution, suspension oremulsion can be used for this purpose.

Suitable free radical initiators are selected from the group comprisingaZo-bis-isobutyronitrile, benzoyl-peroxide, di-tert. butylperoxide, theborotrialkyls and oxygen, and the persulfates in the presence or absenceof ferrous sulfate.

Suitable solvents or dispersants include water, ethers, hydrocarbons,N,N-dimethylformamide, dimethylsulfoxide etc. If desired, thepolymerization can be promoted by photochemical methods.

Generally, the polymerization temperatures vary between about C., as inthe case of borotrialkyl and oxygen, and about +120 C. The polyacrylatesand polymethacrylates of the primary and secondary polyfluoro alcoholsof the Formula 2 and the polyacrylamides and polymethacrylamides of theperfluoropolyether amines can also be obtained from polymericintermediates.

Thus, the polymers may be obtained by transesterification or amidationof the methyl polyacrylate or polymethacrylate by a process analogous tothe transesterification and amidation of the monomeric esters.Particularly, the methyl polyester dissolved in toluene can be reactedwith an excess of polyfiuorinated alcohol, in the presence of a Ti(OiC Hcatalyst or toluenesulfonic acid, or with an excess of apolyfluoropolyether amine.

Either the acrylyl or methacrylyl polychloride can be esterified oramidized in a solution of, for example, dioxane, with thepolyfiuorinated amine or the alcohol in the presence of a basic agent.

While not wanting to be held to any specific theory or mode of operationof the present invention, it is generally believed that the propertiesof the polymers of the present invention result from the presence of thepolyether structure forming the side groups of the polymeric chain. Itis thought that the exceptional flexibility of the polymeric products,even at low temperatures, is due to the rotational freedom of the etheroxygen atoms in the side group wherein each ether oxygen is positionedadjacent to 1 or 2 carbon atoms, as occurs more particularly when thepolyether side chain groups attached to the main polymer chain containone or more di-fluoromethylene oxide units, while thehexafiuoropropylene oxide unit can be either present or not.

These desirable properties also occur in copolymeric products wherein atleast half of the acrylic or methacrylic units are bound to a residuecontaining the linear polyfluoropolyether structure. Said properties aremarkedly enhanced when, in the chains of copolymeric nature, more thanabout 80% of acrylic or methacrylic units are bound to a residuecontaining a linear polyfluoropolyether structure.

The following examples illustrate the present invention:

EXAMPLE 1 A solution of g. of pure acid (B.P.=166-168 C.) diluted in 100cc. of ethyl ether was slowly added dropwise to a 1000 cc. glass flask,provided with a stirrer, a water-cooled reflux condenser, and a droppingfunnel, containing 10 g. of LiAlH dispersed in 500 cc. of anhydrousethyl ether and maintained at 0 C. The temperature was raised until theether refluxed and then the mixture was stirred for 2 hours. At the endof this period, the mixture was cooled to 0 C., and then 50 cc. of H 0and then 50 cc. of 20% H 80 were slowly added dropwise, to decompose anddissolve the solid compounds.

The organic layer was then separated, dried with anhydrous calciumsulfate (Drierite) and, after removal of the ethyl ether bydistillation, the residue was subjected to rectification at atmosphericpressure. A 70 g. fraction having a boiling temperature of 129-131 C.and a density of 09 :1696 was separated. Gas-chromatographic analysisindicated that the component was more than 98% pure. The elementalanalysis of this compound corresponded to the formula: C H' F O The LR.ab

ence of 4.1 g. of triethylamine and cc. of ethyl ether,

was reacted with 8.1 g. of CH =CHCOCl at a temperature of 0 C. Thereaction mass'was maintained for 4 hours at C., after which it waspoured into water.

The organic layer was separated and washed with an.

0.5% solution of NaHCO and then dried with Na SO and rectified in amicrodistiller. At C./ 1 mm. Hg, 15 g. of a product were collected whichpossessed an elemental percentage composition corresponding to'the for'The analysis of the IR. absorption spectrum showed absorptions at 1730cmf and at 1640 cm." that are char-, acteristic of the carboxylic groupand of vinyl unsaturation, respectively, indicating that the product hasthe structure:

At the end of this period, the vial was opened and the' contents werepoured into methanol. A heavy, coagulated product was obtained which wasseparated from the solvent, washed and dried. 8 g. of an amorphous,transparent polymer were obtained. This polymer softened at 30 C. andwas insoluble in ethyl ether, acetone, dioxane, ethyl acetate, anddimethylformamide, while it was soluble in methylpcrfluorobutyrate andphenylfiuoroform. Its intrinsic viscosity determined inphenylfiuoroforrn at 90 C. was 0.15 (100 cc./g.).

A solution of 3% of the polyacrylate in methylperfluorobutyrate wasspread over a clean, degreased glass plate and a film of polymerdeposited on the glass due to slow evaporation of the solvent. Thecontact angle formed on the surface of the film thus obtained wasdetermined for a number of pure liquids of. the n-alkane series having aknown surface tension, e.g.,hexadecar1e and heptane. From these anglesthe value of the surface tension, 'y ='y ==l4 (dyne/cm.), defined as thecritical surface tension, Was calculated by means of the Fowkes method(see F. M. Fowkes in Contact Angle, Wettabilityand Adhesion, Adv. Chem,Series No. 43, A.C.S., Washington (1964), page 99, wherein 'y ascritical surface tension of wetting and 'y as surface tension of solidsubstrate due to London dispersion forces are defined).

A sample of woolen fabric was impregnated with' a solution of 3% of thepolyacrylate in benzotrifluoride, by dipping and wringing out twice, theabsorption in the wet state being 85%. Thereupon the fabric was dried byhanging it in a flowing air oven at 110 C. A sample of the fabric thustreated and containing 1.5% of the polyacrylate was evaluated foroil-repellency using a mixture of 40% by volume of Nujol mineral oil(Saybolt viscosity 360- 390/38 C.) and 60% by volume of n-heptane, at 20C. (see I. H. Simons in Fluorine Chemistry, Academic Pr.,

8 New York (1964), vol. 5, page. 402). The fabricdid not absorb any ofthis mixture.

Another sample of the treated fabric was subjected to a water-repellencytest (AATCC method, No. 22, 1961). The wate'r-repellency value thusdetermined was about '80.

EXAMPLE 2 A sample of 100 g. of

CF -O-(CF -(FF-OY -OIMCOOII acid CF: was reduced with LiAlH, (10 g.) inethyl ether (500 cc.) at 0 C., using the same apparatus and operatingprocedure as described in Example 1.

Using the same procedures described hereinabove, after fractionaldistillation, 60 g. of product were obtained having an elementalanalysis. corresponding to the'formula: C H F O and a boiling pointrange of 166167 C./ 760 mm. Hg. The IR. spectrum showed absorption bandsat 2900-3000 CIILTI; at 1440 cm.- and 3350 cum- The N.M.R. analysisconfirmed the CF30 CFzCFO z-CFzCHzOH structure This product, atconcentrations less than 0.1%, reduced the surface tension of water to18 dyne/cm.

44 g. of the described alcohol werereacted with 15 cc. of acrylylchloride in the presence of 0.5 g. of anhydrous BaCl for 6 hours at 60C. The unreacted acrylyl chloride was removed by distillation and theresidue was washed first with 100 g. of water and ice, and then with a0.5% aqueous solution of NaHCOg. The washed residue was dried over Na SOand distilled under a vacuum of 0.2 mm. Hg. 40 g. of a product werecollected at 60-63 C. The elemental and N.M.R. analyses of the productindicated the formula to be:

20 g. of this product were polymerized by heating for 8 hours at 70 C.,in the presence of 0.05 g. of azo-bisisobutyronitriler 12 g. of apolymer were obtained which was insoluble in acetone and CF Cl-CFCl butsoluble in. phenylfiuoroform' and in methylperfiuorobutyrate. In: the

latter solvent the intrinsic viscosity of 0.28 dL/g. was determined at40 C.

By determining the contact angle with hexadecane on a film of thepolymer spread on a glass plate according to the technique described inExample 1, the surface tension was calculated to be 'y 'y =l5(dyne/cm.).

The oil-repellency test was carried out according to the techniquedescribed in Example 1 on a woolen fabric con taining 1.5 of thepolyacrylate ofl,l-,dihydro'-3,6,9-trioxa-4,7-diperfluoromethyl-undecafluoro-decanol-1.

Thus tested, the fabric was completely repellent towards a mixtureconsisting of 30% by vol. of Nujol mineral oil and 70 by vol. ofn-heptane.

Another sample of the same fabriccontaining 1.5% of the polyacrylate wassubjected to the water repellency test (AATCC method, No. 22, 1961). Awater repellency value of about was thus determined.

EXAMPLE 3 V A sample of 50 g. of

CF30-(CFzCF-O)OF2 COOH in Example 1. 7 g. of the corresponding acrylate,having a boiling point of 95 97 C. at 1 mm. Hg were obtained. Theacrylate was then polymerized at 80 C. for hours in the presence of 0.05g. of benzoylperoxide. The polymers intrinsic viscosity determined inmethylperfluorbutyrate at 40 C. was 0.25 dl./g. The surface tension ofthe polymer was 'y ='y =15.5 (dyne/cm.), as determined on a film of thepolymer according to the Fowkes method, as described in Example 1.

EXAMPLE 4 obtained in Example 3 were reacted with a stoichiometricamount of methacrylyl chloride, under the same conditions as in Example1, to give 6.5 g. of the corresponding methacrylate, having a boilingpoint of 110112 C. at 0.5 mm. Hg. The methacrylate was polymerized at 50C. in presence of 0.2% of azo-bis-isobutyronitrile for a period of 7hours. The polymer which had an intrinsic viscosity of 0.3 dl./g. inmethylperfluorobutyrate at 40 C., possessed a surface tension 'y ='y ofabout 16 (dyne/ cm.) as determined by the Fowkes method as described inExample 1.

A sample of cotton treated with a 3% solution of the polymethacrylate inbenzotrifluoride and dried in a flowing air oven at 110 C. contained 1%of the polymer. This sample was subjected to the oil-repellency testaccording to the technique described in Example 1, and was completelyoil repellent towards a mixture of 30% Nujol and 70% n-heptane.

EXAMPLE 5 100 g. of a mixture of acids having the average formula:

CF 0 C F O m (CF 0 -CF COOH wherein the sum of the indices m and n isfrom 1 to 4, with an average ratio m=n/3, and having an averageequivalent acidimetric weight of 515, were reduced for hours with H at40 atm. on Pt0 in an autoclave at 80 C. The corresponding mixture ofalcohols obtained had a boiling temperature range between 120 C. and 210C. at 755 mm. Hg.

A sample of 80 g. of the mixture of alcohols was esterified by reactingit with 20 g. of acrylyl chloride in the presence of 5 g. of anhydrousBaCl After washing with H 0 and sodium bicarbonate and drying over Na SOthe product was distilled under a vacuum of 0.01 mm. Hg, and a 65 g.fraction was collected, this fraction having a boiling temperature inthe range between C. and 70 C. and having the average formula:

wherein m and n are as defined above.

50 g. of this acrylate mixture were polymerized in the presence ofbenzoylperoxide (0.2 g.) at 80 C., for a period of 12 hours. Afterextraction with ethyl ether, 31 g. of polymer were obtained.

This polymer had a rubbery appearance and was insoluble in dioxane andbutyrolactone and slightly soluble in benzotrifluoride andmethylperfluorobutyrate. A sample of this polymer began to thermallydecompose at 325 C. as determined in air with a 59 ADAMEL thermobalance.

The glass transition temperature of the polymer as determined with aDifferential Scanning Calorimeter P.E. DSC 1 was between 90 C. and 85 C.The surface tension of the polymer was 'y ='y =14.5 (dyne/cm.), asdetermined in accordance with the method described in Example 1.

10 EXAMPLE 6 50 g. of the ketone o F3O(C F2C F-O)2C F20 o 0 Fa (B.P. 136C.) and 5 g. of carbon containing 0.5% of Pd were introduced into a 100cc. Inox steel autoclave. The contents were put under vacuum and then Hwas introduced until the pressure was 50 atms. The mixture was reactedfor 10 hours at 40 C. At the end of the reaction, the hydrogen wasdischarged, the reaction product was filtered from the catalytic residueand the product was then rectified, collecting the fraction that boilsbetween 164- 165 C. at 752 mm. Hg (40 g.).

The LR. and N.M.R. spectra of this product corresponded to the fomula:

30 g. of this alcohol were reacted with 10 g. of acrylyl chloride in thepresence of 2 g. of anhydrous BaCl After hydrolysis of the acyl chloridewith an excess of water and sodium bicarbonate, and drying with Na SO 28g. of the acrylate B.P. 111-113 C. at 15 mm. Hg, were obtained.

25 g. of this acrylate were polymerized in the presence of 0.2 10- g.moles of B(nC H and 2 cc. of oxygen, at 30 C., in 250 cc. ofbenzotrifiuoride.

The monomer solution was 70% polymerized after 8 hours of reaction. Atthis point the polymerization was stopped by blowing in air, and thesolution of the polymer and monomer was used for impregnating a sampleof a cotton fabric. The intrinsic viscosity of the polymer as determinedin phenylfluoroform at C. was 0.2 dl./g.

After wringing and drying in a ventilated oven at 110 C., theoil-repellency test was carried out as described in Example 1. A fabriccontaining about 1.2% of the polyacrylate was completely repellent to amixture of 50% Nujol and 50% by vol. n-heptane.

A film of the polymer was prepared by evaporation of a 5% solution ofthe polymer in methylpenfluorobutyrate on glass. The contact angleformed with hexadecane was then determined and, using the Fowkes method,the value of the surface tension 'y ='y was calculated to be about 13(dyne/cm.).

EXAMPLE 7 40 g. of CF O('CF O) CF COOCH ester dissolved in 50 cc. ofanhydrous ethyl ether were slowly added to a sus pension of 4 g. ofLiAlH in 250 cc. of ethyl ether in a lliter flask provided with a refluxcondenser and mechanical stirrer. Then 20 cc. of CH OH were carefullyadded and then 50 cc. of 25% H 80 were added to dissolve thedecomposition products of the hydride. The organic solution wasseparated, the residue was washed with water and dried over Na SO thenthe ethyl ether was distilled and the residue distilled under vacuum. 32g. of an alcohol having the formula CF O(CF O) CF CH OH and boiling at37-39 C. at 0.5 mm. Hg were collected.

30 g. of this alcohol were reacted with a mixture of g. ofmethylacrylate, 0.5 g. of mercuric sulfate, 1 cc. of H 50 and 0.5 g. ofphenothiazine, in a 250 cc. flask provided with an '8 mm. diameterrectification column, filled with Helipack for a length of 30 cm. Themixture was reacted at a reflux ratio of 5:1, a temperature of 6061 C.,and under a pressure of 750 mm. Hg. During the reaction, a mixture ofmethanol and methyl acrylate Was withdrawn. Lastly, the excess ofmethylacrylate was removed by distillation. The1,l-dihydro-3,5,7,9-tetraoxa perfluorodecanol-l-acrylate was thendistilled under vacuum and the fraction boiling at 6065 C. and 0.3 mm.Hg was collected.

11 e 20 g. of the acrylate comprising this fraction were polymerized inthe presence of 0.2 g. of benzoylperoxide at a temperature of 80 C., for5 hours. The polymer obtained had a gummy consistency and an intrinsicviscosity of 0.31 dL/g. in methylperfiuorobutyrate at 40 C.

The surface tension 'y ='y of the polymer was 13.5 (dyne/cm.), asdetermined on a film of the polymer obtained from a 3% solution'of thepolymer in benzotrifluoride, using the Fowkes method. A sample of cottonfabric was impregnated by dipping in a 3%. solutionof the polyacrylatein methylperfiuorobutyrate. After wringing and drying the sample fabricat 110 C. in a ventilated oven, the fabric, containing 1.2% of polymer,was tested for oil-repellency according to the method described inExample 1. The fabric was completely oil-repellent towards a mixture of50% by volume of Nujol and 50% by volume of n-heptane. 7

EXAMPLE 8 The ketone having the formula V CF30 CF -CF-O-(JF COCF;

B.P.=85-86 C.) was distilled over P 0.12 g. mole of the freshlydistilled ketone was introduced into a 500 cc. glass flask which wasprovided with a stirrerand a dropping funnel, contained a mixture of 7g. of anhydrous potassium fluoride in 100 cc. of .anhydrousN,N-dimethylformamide and the contents of which were thermostaticallymaintained at 0 C.

This mixture was treated for 2 hours at 0 C., and then, over a 3 hourperiod, the temperature was raised to 60 C., to give a homogeneoussolution of the pot-assium perfiuoroalcoholate in the solvent.

The solution was then again cooled to 0 C., after which 0.12 g. mole of.acrylyl chloride was slowly added.

During the addition of the acrylyl chloride, potassium chloride formedand precipitated from the solution. At the end. of the addition, thetemperature was again raised to 50 C. over a period of 3 hours in orderto complete the reaction. Thereupon the mixture was poured into 500 g.of water and ice, the organic layer was washed with water and then,after drying over Na SO the mixture was rectified. 40 g. of a productboiling :at 70-72 C. under 15 mm. Hg were collected. The elementalpercent analysis, the LR. spectrum and the N.M.R. spectrum indicated thestructure of the product to be:

CF3O(CFzCFO) -CO-CH=CH which may also be written asCFQOOFZ-CF-0CF2OF(CF3)OCOCH=CHI,

g. of this acrylate were polymerized by heating for 10 hours at 80 C. inthe presence of 0.2 g. of benzoylperoxide. After precipitation inmethanol and drying under a vacuum of mm. Hg at 50 C., 6 g. of a polymerwere obtained, this polymer having an intrinsic viscosity as determinedin methylperfiuorobutyrate at 40 C. of 0.26 dl./g. A film of thispolymer was deposited on a glass plate from a 3% solution of the polymerin benzot-rifiuoride. The contact angle with hexadecane on this film wasthen determined. The surface tension, calculated according to the Fowkesmethod as described in Example 1, was 'Y 12.8 (dyne/=cm.).

EXAMPLE 9 100 g. of an equimolar mixture of acids having the formulae CFOCF OCF COOH and CF O(CF O) CF COOl-l the mixture having a boiling pointbetween 135 C. and 156C. at a pressure of 755 mm. Hg, dissolved in100cc. of anhydrous ethyl ether, were added to a mixture of The contentsof the flask were then poured into water,

and the organic phase was washed with. water and then dried with Na SOThe solvent was removed by distillation. On distillation at atemperature of from 105 to 135 C., g. of a mixture of the alcohols wereobtained. 50 g. of this mixture were reacted at 50 C. with 30 g. ofacrylyl chloride in the presence of 2 g. of anhydrous BaCl After 5 hoursof reaction, the reaction mass was poured into water and sodiumbicarbonate, and the organic solution was washed with Water and then.dried over Na SO The residue was rectified, and 30 g. of a fractionboiling between 35 C. and 45 C. at 15 mm. Hg were collected. 10 g. ofthis fraction were polymerized in solution in 20 cc; ofmethylperfluorobutyrate in the presence of 0.2 g. ofazo-bis-isobutyronitrile for 15 hours at 60 C. The polymerization yieldwas 70% as determined by gravimetric analysis.

The. polymer had an intrinsic viscosityas determined inmethylperfluorobutyrate at 40 C. of 0.35 dl/g. and a surface tension 'y='y of 14 (dyne/cm.) according to the Fowkes method described in Example1.

7 EXAMPLE 10 g. of a mixture of 90 parts of the ketone having theformula and 10 parts of the ketone having the formula the mixture havinga boiling range of from 85 C. to C. (755 mm. Hg), were slowly introducedinto a 500 cc. glass flask containing 14.5 g. of KF. This mixture wasdispersed, with stirring, in 300 'cc. of anhydrous dimethoxyethane,thermostatically stabilized at 0 C.

The mixture was reacted at temperatures between about 0 C. and 50 C.',until the reaction mixture was completely dissolved (5 hours); Themixture was cooled to 0 C. and 21 g. of acrylyl chloride were added withstirring over a 1 hour period. The solution was then allowed to reactfor3 more hours at 50 C.

The mixture was then poured into water and ice and the organic layer,after repeated washing with water and drying over Na SO was rectified.The fraction boiling between 60 and 80 C. under a vacuum of 15 mm. Hg(60 g.) was collected.

50 g. of this mixture of acrylates were placed under a nitrogenatmosphere in a quartz test tube immersed in a water baththermostatically stabilized at a temperature of 30 C. The mixture wasthen polymerized by U.V. radiation using an original Hanau Q 81 quartzU.V. lamp, placed inside the water bath and arranged parallel andcoaxially' to the test tube. 7

After 5 houurs exposure, the radiation was stopped and the unreactedmonomer (20 g.) was removed by evaporation at 80 C. under a 1 mm. Hgvacuum. The polymer, whose intrinsic viscosity inmethylperfiuorobutyrate at 40 C. was of 0.15 dl./g., was dissolved in 1liter of methylperfiuorobutyrate. Samples of cotton and wool fabricsimpregnated with this solution were completely repellent towards aliquid mixture consisting of 60 parts by volume of Nujol oil and 40parts of n-heptane.

13 EXAMPLE 11 3 cc. of freshly distilled acrylyl chloride and a solutionof 50 mg. of azo-bis-isobutyronitrile in 3 cc. of anhydrous dioxane,were introduced into a 50 cc. glass test tube under an atmosphere of drynitrogen. The mixture was thermostatically stabilized at 50 C. and wasthen allowed to react for 50 hours. At the end of the polymerization,the dioxane and the unreacted monomer were evaporated under vacuum. 2 g.of polymer were obtained, which were dissolved in 25 cc. of anhydrousdioxane and there admixed with a solution of 12 g. of the alcohol havingthe formula CF O-(C F O) CF CH OH in 10 cc. of anhydrous dioxane whichcontained 2.5 g. of triethylamine.

The solution was reacted for 5 hours at reflux temperature. The reactionmixture was then poured into methanol and 12 g. of polymer wereobtained. This polymer possessed a carbon content of 26.2%, whichcorresponds to a polyacrylate in which about 95% of the carboxyl groupsare esterified with the fluoropolyether alcohol.

This polymer was soluble in methylperfluorobutyrate. A 0.5% solution ofthe polymer in methylperfluorobutyrate at 30 C. possessed a viscosity of0.35 (100 cc./g.).

The contact angle of hexadecane on a film of this polymer was determinedand the surface tension, calculated according to the Fowkes method asdescribed in Example 1, was 'y ='y =l6.9 (dyne/cm.).

EXAMPLE 12 2 g. of methylpolyacrylate, cc. of toluene, 0.1 g. of Ti(OiCH and g. of the alcohol having the formula CF O(C F O) CF CH OH wereintroduced into a 50 cc. flask equipped with an 8 x 300 mm.rectification column filled with Fenske rings. The mixture was refluxedfor 2 hours, after which liquid was drawn off from the head of thecolumn at a rate of about 0.5 cc./hour. After 10 hours, 5 cc. of tolueneand 5 g. of the polyether alcohol were added to the flask and thereaction was carried out for another 10 hours in the presence of 0.1 g.of fresh catalyst. At the end of this period, the reaction mass waspoured into methanol. After drying, 11.5 g. of polyacrylate whichpossessed a carbon content of 26.5% were obtained, indicating that 90%of the carboxyl groups were esterified with the fluorinated alcohol.This polymer showed an intrinsic viscosity of 0.55 dl./ g. as determinedin methylperfluorobutyrate at 40 C.

The contact angle with heptane on a film of this polymer, obtained froma solution of the polymer in methylperfluorobutyrate, was measured. Asurface tension of v =v =l8 (dyne/ cm.) was calculated using the Fowkesmethod.

EXAMPLE 13 A solution of 30 g. of the ester having the formula CF O(C FO) CF COOCH in 50 cc. of CFgCl-CFCI was slowly added over a 3 hourperiod to a mixture of 2 g. of LiAlH and 250 cc. of anhydrous ethylether in a 500 cc. flask provided with a reflux condenser and amechanical stirrer.

The mixture was reacted at 0 C. for 3 hours and then for 3 hours atreflux. Thereafter the excess LiAlH was decomposed with water and 10% H80 The ether layer was washed with water until the washings wereneutral. The organic solution was dried over Na SO the ethyl ether wasremoved by distillation and the residue was vacuum distilled. 24 g. of afraction having a B.P. between 130 C. and 135 C. at 0.2 mm. Hg wereobtained. The elemental analysis and the LR. spectrum of the fractioncorresponded to the formula CF O(C F O') CF CH OH.

10 g. of this alcohol was reacted with 1.5 g. of CH =CHCOCl in 30 cc. ofethylether in the presence of 3 CC. Of (C2H5)3N.

The reaction was carried out under stirring at 0 C. for 2 hours.Thereafter, the entire reaction mixture was poured into 50 g. of icewater and the organic solution was separated and dried over Na SO Thesolvent was 14 distilled under vacuum, leaving the pure acrylic esterasthe residue. The LR. spectrum of the residue showed absorptionsattributable to the carboxy group and vinyl saturation characteristic ofthe structure.

5 g. of the acrylic ester were polymerized in solution in 20 cc. ofmethyl perfluorobutyrate in the presence of 0.05 g. ofazo-bis-isobutyronitrile for 15 hours at 60 C. At the end of thereaction, the polymer was coagulated by pouring the reaction mixtureinto 100 cc. of acetone. The polymer was then separated and dried. 3.2g. of dried polymer having an intrinsic viscosity as determined inmethylperfluorobutyrate at 40 C. of 0.22 dl./ g. were obtained.

A film of this polymer was obained by evaporation of a 2% solution ofthe polymer in methyl perfluorobutyrate on a glass plate.

From the contact angle data from this film, a surface tension of 'y =7of about 13 (dyne/cm.) was calculated, using the Fowkes method.

EXAMPLE 14 A sample of 30 g. of a mixture of acids having the averageformula CF 0(CF O) ,(C F O) CF COOH, in which the sum of the indices n+mis from 2 to 14 and the value of the average of the ratio of mr/n isabout 3, and which has an average equivalent acidimetric weight of 860,was added to a mixture of 100 cc. of ethyl ether, 30 cc. of CF Cl-CFCland 2 g. of LiAlH The reaction was carried out for 3 hours at atemperature of 0 C. The temperature was then raised to 35 C.

After 4 hours at this temperature, the excess of LiAlH was decomposedwith water and 10% H The organic layer was separated, washed with wateruntil the washings were neutral, and then dried over Na SO' The solventswere removed by distillation, leaving behind the mixture of thecorresponding alcohols as a residue.

10 g. ofthe mixture of alcohols in the mixture of 20 cc. of ethyl ether,10 cc. of CF CI-CFCI and 3 cc. of (C H N, were reacted at 0 C. with 1.3g. of

CH =CHCOCl dissolved in 10 cc. of ethyl ether.

The reaction was carried out at 0 C. for 2 hours. The reaction productwas poured into 50 g. of ice water, and the organic phase was separatedand washed with water util the washings were neutral. The solvents wereremoved by evaporation, leaving as a residue the mixture of fluorinatedacrylic esters.

5 g. of this mixture of acrylic esters dissolved in 10 cc. of a 1:1mixture of ethylacetate and CF Cl-CFCl were polymerized in the presenceof 0.1 10 g. moles of B(iC H and 1 cc. of oxygen at 30 C. for 10 hours.

The polymer thus obtained was coagulated by pouring the mixture into 100cc. of acetone. After washing with acetone and drying 2.5 g. of polymerhaving an intrinsic viscosity as determined in phenylfluoroform at C. of0.32 dl./ g. were obtained.

A polymer film was prepared by evaporating a 1% solution of the polymerin methylperfluorobutyrate on a glass plate. Using the contact angledata obtained from the film, a surface tension 'y =about 12 (dyne/cm.)was calculated using the Fowkes method as described in Example 1.

EXAMPLE 15 54 g. of the perfluoropolyether ketone having the formula CFO(C F O) CF COCF were slowly added to a suspension of 3.5 g. ofanhydrous KF in 50 cc. of dimethylformamide at a temperature of 0 C.

After 2 hours at room temperature, the solution became homogeneous; itwas then cooled to 0 C. and a solution of 5.4 g. of CH =CHCOCl in 10 cc.of dimethylformamide was added. This mixture was allowed to react for 1hour at C. and for 2 hours at room temperature. The reaction mixture wasthen poured into 50 g. of ice water, and the organic layer was separatedand Washed twice with 10 cc. of water. The organic solution was thendiluted with 50 cc. of CF Cl-CFCl and was dried over Na SO After thesolvent was evaporated, 35 g. of a residue were obtained. The IR.spectrum corresponded to the structure CF O(C F O) COCH=CH Afterdissolving g. of the acrylate in 10 cc. of a mixture of 50% of CFCl-CFCl and ethylacetate. the acrylate was polymerized with 0.15 110 g.moles of B(iC H in the presence of 1.5 cc. of oxygen at 30 C. for 6hours.

At the end of the reaction, the polymer was coagulated by pouring 100cc. of acetone into the reaction mixture. After'filtering and drying,4.1 g. .of polymer were obtained. This polymer having an intrinsicviscosity as determined in phenylfluoroform at 90 C. of 0.25 dL/g. Afilm was prepared from a 1% solution of this polymer inmethylperfiuorobutyrate. The surface tension dyne/ cm.) was determinedfrom the contact angle data from the film using the Fowkes method.

EXAMPLE 16 55 g. of

(B.P. 161-162 C.) dissolved in 50 cc. of ethyl ether were introducedinto a 100 cc. glass flask provided with a reflux condenser and adipping pipe for feeding gases. A flow of NH gas was bubbled into thissolution at 0 C. for 30 minutes. At the end of the bubbling, the solventand the methyl alcohol were removed by evaporation. The solution wasthen diluted with an additional. 20 cc. of ethyl ether and thissolution, containing the amide, was added with stirring, to a suspensionof 6 g. of LiA1H in300 cc. of anhydrous ether, at 0 C. over a one hourperiod. The mixture was then refluxed for 3 hours.

After this period, the mixture was cooled to 0 C. and 10 cc. of methanolwere added to it over a minute period. Then the mixture was poured into100 g. of ice and water and, to the suspension thus obtained, g. of a40% NaOH'solution were added, while stirring the sus: pension 'to assurecomplete dissolution of the inorganic salts.

The ether layer was then separated and the inorganic layer was extractedwith an additional 50 cc. of ethyl ether. Theether layers were combinedand dried over K CO The solvent was then evaporated and the residuedistilled. 27 g. ofa fraction boiling at 152-153 C. were obtained. Theproduct was assigned the structure on the basis of the LR. absorptionsdue to the NH stretching (3200-3400 cmf and CH stretching (2900 cmr andNH bending (1625 cmi' absorptions. No absorptions in the l7001800 cm.-zone characteristic of the starting ester carbonyl group and of theamide, were observed.

4.5 cc. of acrylyl chloride dissolved in. 40 cc. ofether were added to asolution of 20 g. of the amine having the formula CF O(C F O) CF CH NHand 8 cc. of triethylamine in 200 cc. of ethyl ether, maintained at 0 C.

This mixture was reacted for 3 hours at 0 C. and then for 3 hours at C.,with stirring, during which time the chlorohydrate of triethylamineseparated out of the mixture. It was filtered from the aminechlorohydrate, and the ether solution was washed with water andthen'dried over Na SO After concentration and distillation, 18 g. of afraction having a B.P. range between 8590 C. at 0.5 mm. Hg (23 C./760mm.) were obtained.

on the basis of the LR. absorptions due to NH bonds in the 3200 cmrzone, to the CH bonds at 3000 CHM-1,

, to the amide group in the 1670 and 1550 cm. zone, and

the absorptions in the 1600-1650 CIIL'I zone due to the NH and thedouble bond. 7

10 g. of the acrylamide were polymerized under a nitro-. gen atmosphereat 70 C., in the presence of 0.04 g. of azo-bis-isobutyronitrile. After20 hours, the reaction mass was poured into a 1:1 mixture ofmethanol'and ether. After separation of the solvent and drying, 6 g. ofpolymer were obtained, which polymer was insoluble in hydrocarbons,ketones, ether,and N,N-dimethylformamicle, and soluble inmethylheptafluorobutyrate. V

The polymer had the following elemental analysis: C=2'6.1%; H =l.08%(calculated values: O=26..12%; H=1.09). The intrinsic viscosity was 0.2(100 cc./g.) at 30 C., as determined on a 0.5% solution of the polymerin C3F7COOCH3.

A film of the polymer was deposited on a glass plate by evaporating a 1%solution of the polymer. The contact angle with hexadecane was measured,and the surface tension calculated accordingto the Fowkes method was 'y='y =l3 dyne/cm.

A 10 x 10 cm. sample of cotton fabric was impregnated using a 3%solution. of the polymer in methylperfiuorobutyrate. The driedfabriccontained 1% by weight of thepolymer. The fabric sample thusprepared possessed a repellency rating of towards a mixture of 40% Nujoloil and 60% n-heptane (by volume). The same sample of fabric wasimpregnated and stained with a 10% by weight solution of olive oil inether. The ether was then removed by evaporation.

After drying for 1 hour, the fabric was washed by mechanically flappingthe fabric in 200 cc. of a 05% solution of Dash detergent solution at 22C. (according to the methods outlined by J. C. Stewart and C. S. Whewell in Textile Research Journal, 20, 912, 1960', and by K. Durhan inSurface Activity and Detergency, Mac- Millan Co., London 1961, page229).

After 30 minutes, by washing the fabric with water, drying andextracting with hot ether, it-was determined that the oil had beencompletely removed during the washing.

This sample was again tested for oil repellency using the standard oilrepellency test described hereinabove. The oil repellency rating thusdetermined was 90. This indicates excellent retention of the anti-stainproperty of the fabric.

' EXAMPLE 17 10 g. of this product were polymerized in the presence of0.050 g. of benzoylperoxide at 70 C. after 20 hours,

the mixture was Washed with a 1:1 mixture of methanol and ether anddried to constant weight. 5.1 g. of polymer were obtained. This polymerhaving the following ele (calculated mental analysisz' (D -27.7%;LIT-1.4%. C=27.6%; H=1.42% A filr'n'of'the polymer was deposited on aglass plate by evaporation of a'1% solution of the polymer in CFCl -CFCI the intrinsic viscosity of 1 7 which polymer determined at 20 C., was0.25 dl./g., and the contact angle with hexadecane was measured. Thesurface tension determined according to the Fowkes method as describedin Example 1 was 'y 'y= 18 (dyne/ cm.).

EXAMPLE 18 A slow flow of gaseous NH was introduced over a 30 minuteperiod into a 100 cc. glass flask provided with a dipping pipe and witha reflux condenser and containing 10 g. of CF O(CF CF CO0CH (B.P. =93 C.at 55 mm. Hg) dissolved in 50 cc. of ethyl ether. At the end of thisperiod, the excess NH ethyl ether and methanol were evaporated. Thesolution was then diluted with an additional 20 cc. of ether and thediluted solution was added over a 1 hour period to a suspension of 2 g.of LiAlH in ethyl ether, maintained with stirring, at 0 C. The mixturewas refluxed for an additional 3 hours. Then 5 cc. of methanol wereadded to the solution and then the solution was poured into 100 g. ofwater and ice. The organic layer was separated and dried over K CO Theether was removed by evaporating and the residue was distilled. 6 g. ofa fraction having a B.P. of 95 -98 C. at 30 mm. Hg were collected. TheIR. spectrum corresponded to the structural formula 5 g. of this aminewere reacted with 1.5 cc. of acrylyl chloride in cc. of ethylethercontaining 3 cc. of triethylamine for 3 hours at 35 C. The reactionmixture was then filtered from the amine chlorohydrate, and the ethersolution was washed with water and dried over Na SO The solvent was thenevaporated and the residue distilled. 3 g. of a fraction boiling at 9598C. at 0.5 mm. Hg were collected. The IR. spectrum corresponded to thestructural formula:

2 g. of this monomer were polymerized under a nitrogen atmosphere in thepresence of 0.02 g. of azo-bis-isobutyronitrile for 10 hours at atemperature of 60 C. After washing with a 1:1 mixture of methanol andether and drying to constant weight, 1.1 g. of a polymer were obtained.The elemental analysis of this product was as follows: C=25.2%; H=1.3%(calculated O=%.; H=1.25%).

A film of this polymer was deposited on a glass plate from a 1% solutionof the polymer in methylperfluorobutyrate the intrinsic viscosity ofwhich polymer as determined at 40 C. was 0.4 dl./g., and the contactangle with hexadecane measured. The surface tension determined accordingto the Fowkes method as described in Example 1 was 'y ='y -=14(dyne/cm.). A sample of cotton fabric impregnated with 1% by weight ofpolymer and subjected to the oil-repellency test was completelyrepellent to a mixture of 40% Nujol oil and 60% by volume n-heptane.

EXAMPLE 19 A solution of 20 cc. of

omo-orr-oro-o FzCOOCH;

having a B.P. of 123 l25 C. in ethyl ether was introduced into a 100 cc.glass flask provided with a clipping pipe for the inlet of gases and areflux condenser. A flow of gaseous CH -NH produced from the reaction of50 cc. of a aqueous solution of the amine with NaOH solution was slowlybubbled into the flask. After one hour, at the end of the reaction, theexcess of amine, ethyl ether and methanol was evaporated. The remainingether-amine solution was added dropwise with stirring to a suspension of5 g. of LiAlH in 200 cc. of ether over a 1 hour period while maintainingthe suspension at 0 C. The reaction mixture was then refluxed for anadditional 5 hours and then cooled to 0 C.

10 cc. of methanol were added and the whole was poured into 100 g. ofice and water. 10 cc. of a 40% solution of NaOH were added to thismixture and, after dissolving the inorganic derivatives, the ether layerwas separated, the ether evaporated and the residue distilled. 20 g. ofa fraction boiling at 114-l16 C. was obtained. The LR. spectrum of thisfraction contained absorptions for the stretching of the NH bonds at3350 cm. and the C--H bonds at 2900 cmr Based on the LR. spectrum, theproduct was assigned the formula:

To a mixture of 16 g. of this secondary amine 6 cc. of triethyl amineand 50 cc. of ether, cooled to 0 C., 4 cc. of acrylyl chloride wereadded over a 1 hour period. The mixture was allowed to react for another3 hours at 35 C. Thereafter, the amine chlorohydrate was filtered fromthe reaction mixture, the solvent was evaporated and the filtratedistilled. 12 g. of a fraction boiling at 55- 58 C./0.5 mm. Hg (182 C.at 760 mm. Hg) were obtained. The LR. spectrum of this fractionindicated it had the formula 5 g. of this monomer, diluted in 5 cc. ofethylacetate, were polymerized in a glass vial for 15 hours, in thepresence of 0.05 g. of B(iC H and 1 cc. of oxygen, at a temperature of 0C. At the end of the polymerization, the polymer was precipitated byadding a 1:1 mixture of methanol and ether. After filtering and dryingto constant weight, 3 g. of a polymer were obtained. This polymer wasinsoluble in hydrocarbons and other non-fluorinated polar solvents suchas ketones, ethers and esters, but was solube inmethylperfluorobutyrate, in which solution the polymer showed at 40 C.an intrinsic viscosity of 0.55 dL/g.

A film of this polymer was deposited on a glass plate by evaporating a1% solution of the polymer, and the contact angle with dodecane wasmeasured. The surface tension calculated according to the Fowkes methodas described in Example 1 was 'y ='y, 17 (dyne)/cm.).

EXAMPLE 20 30 g. of a mixture of acids having an average formula CF O(CFO) (C F 0) CF -COOH, wherein the sum of the indices m+n is from 2 to 14and and the average value of the ratio mm is about 3, and having anaverage equivalent acidimetric weight of 860, were esterified withdiazomethane.

The esters were then dissolved in 100 cc. of a 50% mixture of CF Cl-CFCland ethyl ether. The solution was then cooled to 0 C. and anhydrous NHwas bubbled through it for 30 minutes until the amidation reaction wascomplete as determined by LR. spectrography. The excess ammonia wasevaporated and solvents and the methanol were evaporated under vacuum.

The amide mixture was dissolved in 50 cc of a 50% mixture of ethyl etherof CF Cl-CFCl and this solution was then added dropwise over a 2 hourperiod to a suspension of 2 g. of LiAlH in 200 cc. of ethyl ethermaintained at 0 C. This mixture Was then further reacted at 35 C. for 6hours. Thereupon, the LiAlH excess was decomposed with a 20% aqueoussolution of NaOH. The amine mixture was then separated, washed withwater and dried over K CO After evaporation of the solvents, 25 g. ofresidue were obtained comprising a mixture of amines having the formulaCF 0(C F O) (CF -O) CF CH NH with the values of the indices m and 11corresponding to those of the starting mixture, as determined by N.M.R.

19 ether and CF C1-CFCl in the presence of a stoichiometric amount of (CH N at C. The mixture was reacted at 0 C. for 3 hours and then for 2hours at room temperature.

The reaction mixture was then poured into 100 g. of ice water, and theorganic layer was separated and washed with water, and was then driedover Na SO The solvents were then evaporated by distillation undervacuum. The residue obtained was a mixture of acrylamides as determinedby I.R.,analysis.

5 g. of this mixture were dissolved in cc. of a 50% mixture ofethylacetate and CFCl -CF Cl and were then polymerized in a glass vialwith 0.1 10- g. mole of B(iC H in the presence of 5 cc. of dry air atroom temperature for 6 hours.

The polymer was coagulated with an excess of acetone. The coagulate waswashed with acetone and then dried by heating under vacuum at 30 C. 2.1'g. of product were obtained, this product having an intrinsic viscosityas determined in methylperfiuorobutyrate at 40 C. of 0.25 dl./ g. A filmof this polymer was prepared by evaporation of a 1%methylperfluorobutyrate solution of the polymer on a glass plate.Thesurface tension was 'Ysd='Yc=13 dyne/cm. calculated according to theFowkes method as described in Example].

Variations'can, of course, be made Without departing from the spirit andscope of this invention.

Having thus described our invention, what we desire to secure by LettersPatent and hereby claim is:

1. A polyfluorinated polyether having the formula:

wherein:

C F represents a group obtained by the opening of the doublebond of ahexafluoropropene molecule,

C F O-- and -CF O- are repeating oxyperfluoroalkylene units which, whensimultaneously present, are distributed randomly along the chain,

m is zero or an integer from 1 to 20, n is an integer from 1 to 20, thesum of m+n is an integer from 1 to 20, A is a CF or CF O-CE(CF terminalgroup, Z is CX(Y)O wherein X is a hydrogen or fluorine atom, Y is a CFgroup or may be hydrogen but only when X is also hydrogen, and R ishydrogen or CH 2. The polyfluorinated polyether of claim 1 wherein Z isCH O.

3. The polyfluorinated polyether of claim 1 wherein Z is CH(CF )O.

4. The polyfluorinated polyether of claim 1 wherein Z is CF(CF )O-.

References Cited UNITED STATES PATENTS 3,385,882 5/1968 Tullio 260-486 H3,544,537 12/1970 Brace 260--486 H LORRAINE A. WEINBERGER, PrimaryExaminer Y P. I. KILLOS, Assistant Examiner U.S. Cl. X.R.

2528.9; 260-895 H, 89.7 R, 561 N, 584 B, 615 BF gg-g UNITED STATESPATENT oFmcE CERTIFICATE 6F CUEC'MCN Patent No. 3 766, 251 Dated October16, 1.973

Inventor(s) Gerardo Caporiccio and Ezio Stre'pparola It is certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

Column 3, lines 11-12;

"CF 0(CF CF-O) -CF 011 021" 3 3 3 2 should read CH OH CF Column 3, line33: "B-hydro-" should read Z-hydro- Column 3, lines 52-53: "of themethacrylic acid" should read of acrylic and methacrylic acid Column 5,lines 39-40: N CP COW should read NW CF CO Column 8, line 56: "70 by"should read 70% by Column 18, line 42: 'ysd yo 1?" should read-'ysd=7c=l7-.

Signed and sealed this 26th 'dayof March" 1974.

(SEAL) Attest:

EDWARD M.PLETCHER,JR. c. MARSHALL DANN Attesting Officer Commissioner ofPatents L .J

